Singh 

et al. J Nanobiotechnol (2018) 16:84

https://doi.org/10.1186/s12951-018-0408-4 Journal of Nanobiotechnology

REVIEW Open Access

‘Green’ synthesis of metals and their oxide

nanoparticles: applications for environmental
remediation
Jagpreet Singh1, Tanushree Dutta2, Ki‑Hyun Kim3*, Mohit Rawat1, Pallabi Samddar3 and Pawan Kumar4* 

Abstract 
In materials science, “green” synthesis has gained extensive attention as a reliable, sustainable, and eco-friendly pro‑
tocol for synthesizing a wide range of materials/nanomaterials including metal/metal oxides nanomaterials, hybrid
materials, and bioinspired materials. As such, green synthesis is regarded as an important tool to reduce the destruc‑
tive effects associated with the traditional methods of synthesis for nanoparticles commonly utilized in laboratory and
industry. In this review, we summarized the fundamental processes and mechanisms of “green” synthesis approaches,
especially for metal and metal oxide [e.g., gold (Au), silver (Ag), copper oxide (CuO), and zinc oxide (ZnO)] nanoparti‑
cles using natural extracts. Importantly, we explored the role of biological components, essential phytochemicals (e.g.,
flavonoids, alkaloids, terpenoids, amides, and aldehydes) as reducing agents and solvent systems. The stability/toxicity
of nanoparticles and the associated surface engineering techniques for achieving biocompatibility are also discussed.
Finally, we covered applications of such synthesized products to environmental remediation in terms of antimicrobial
activity, catalytic activity, removal of pollutants dyes, and heavy metal ion sensing.
Keywords:  Green synthesis, Metals, Metal oxide nanoparticles, Natural extracts

Introduction from simpler molecules) also includes many meth-

Over the last decade, novel synthesis approaches/meth-
ods for nanomaterials (such as metal nanoparticles,
quantum dots (QDs), carbon nanotubes (CNTs), gra-
phene, and their composites) have been an interesting
area in nanoscience and technology [1–9]. To obtain
nanomaterials of desired sizes, shape, and functionalities,
two different fundamental principles of synthesis (i.e., top
down and bottom up methods) have been investigated in
the existing literature (Fig.  1). In the former, nanomate-
rials/nanoparticles are prepared through diverse range
of synthesis approaches like lithographic techniques,
ball milling, etching, and sputtering [10]. The use of a
bottom up approach (in which nanoparticles are grown
*Correspondence: kkim61@hanyang.ac.kr; pawannano10@gmail.com
3
Department of Civil & Environmental Engineering, Hanyang University,
Seoul 04763, South Korea
4
Department of Nano Science and Materials, Central University
of Jammu, Jammu, J & K 180011, India
Full list of author information is available at the end of the article
ods like chemical vapor deposition, sol–gel processes,
spray pyrolysis, laser pyrolysis, and atomic/molecular
condensation.
Interestingly, the morphological parameters of nano-
particles (e.g., size and shape) can be modulated by
varying the concentrations of chemicals and reaction
conditions (e.g., temperature and pH). Nevertheless, if
these synthesized nanomaterials are subject to the actual/
specific applications, then they can suffer from the fol-
lowing limitation or challenges: (i) stability in hostile
environment, (ii) lack of understanding in fundamental
mechanism and modeling factors, (iii) bioaccumulation/
toxicity features, (iv) expansive analysis requirements,
(v) need for skilled operators, (vi) problem in devices
assembling and structures, and (vii) recycle/reuse/regen-
eration. In true world, it is desirable that the properties,
behavior, and types of nanomaterials should be improved
to meet the aforementioned points. On the other hand,

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Singh et al. J Nanobiotechnol (2018) 16:84
Fig. 1  Different synthesis approaches available for the preparation of metal nanoparticles
these limitations are opening new and great opportuni-
ties in this emerging field of research.
To counter those limitations, a new era of ‘green syn-
thesis’ approaches/methods is gaining great attention in
current research and development on materials science
and technology. Basically, green synthesis of materials/
nanomaterials, produced through regulation, control,
clean up, and remediation process, will directly help
uplift their environmental friendliness. Some basic prin-
ciples of “green synthesis” can thus be explained by sev-
eral components like prevention/minimization of waste,
reduction of derivatives/pollution, and the use of safer
(or non-toxic) solvent/auxiliaries as well as renewable
feedstock.
‘Green synthesis’ are required to avoid the produc-
tion of unwanted or harmful by-products through the
build-up of reliable, sustainable, and eco-friendly syn-
thesis procedures. The use of ideal solvent systems and
natural resources (such as organic systems) is essential
to achieve this goal. Green synthesis of metallic nano-
particles has been adopted to accommodate various
Page 2 of 24
biological materials (e.g., bacteria, fungi, algae, and
plant extracts). Among the available green methods of
synthesis for metal/metal oxide nanoparticles, utiliza-
tion of plant extracts is a rather simple and easy process
to produce nanoparticles at large scale relative to bacte-
ria and/or fungi mediated synthesis. These products are
known collectively as biogenic nanoparticles (Fig. 2).
Green synthesis methodologies based on biologi-
cal precursors depend on various reaction parameters
such as solvent, temperature, pressure, and pH con-
ditions (acidic, basic, or neutral). For the synthesis of
metal/metal oxide nanoparticles, plant biodiversity
has been broadly considered due to the availability
of effective phytochemicals in various plant extracts,
especially in leaves such as ketones, aldehydes, fla-
vones, amides, terpenoids, carboxylic acids, phenols,
and ascorbic acids. These components are capable of
reducing metal salts into metal nanoparticles [11]. The
basic features of such nanomaterials have been investi-
gated for use in biomedical diagnostics, antimicrobials,
Singh et al. J Nanobiotechnol (2018) 16:84
Fig. 2  Key merits of green synthesis methods
catalysis, molecular sensing, optical imaging, and
labelling of biological systems [12].
Here, we summarized the current state of research
on the green synthesis of metal/metal oxide nanopar-
ticles with their advantages over chemical synthesis
methods. In addition, we also discussed the role of
solvent systems (synthetic materials), various biologi-
cal (natural extracts) components (like bacteria, algae,
fungi, and plant extracts) with their advantages over
other conventional components/solvents. The main
aim of this literature study is to provide detailed mech-
anisms for green synthesis and their real world envi-
ronmental remediation applications. Overall, our goal
is to systematically describe “green” synthesis proce-
dures and their related components that will benefit
researchers involved in this emerging field while serv-
ing as a useful guide for readers with a general interest
in this topic.
Biological components for “green” synthesis
Innumerable physical and chemical synthesis
approaches require high radiation, highly toxic reduct-
ants, and stabilizing agents, which can cause pernicious
effects to both humans and marine life. In contrast,
green synthesis of metallic nanoparticles is a one pot
or single step eco-friendly bio-reduction method that
requires relatively low energy to initiate the reaction.
This reduction method is also cost efficient [13–19].
Page 3 of 24
Bacteria
Bacterial species have been widely utilized for com-
mercial biotechnological applications such as biore-
mediation, genetic engineering, and bioleaching [20].
Bacteria possess the ability to reduce metal ions and are
momentous candidates in nanoparticles preparation
[21]. For the preparation of metallic and other novel
nanoparticles, a variety of bacterial species are utilized.
Prokaryotic bacteria and actinomycetes have been
broadly employed for synthesizing metal/metal oxide
nanoparticles.
The bacterial synthesis of nanoparticles has been
adopted due to the relative ease of manipulating the bac-
teria [22]. Some examples of bacterial strains that have
been extensively exploited for the synthesis of bioreduced
silver nanoparticles with distinct size/shape morpholo-
gies include: Escherichia coli, Lactobacillus casei, Bacillus
cereus, Aeromonas sp. SH10 Phaeocystis antarctica, Pseu-
domonas proteolytica, Bacillus amyloliquefaciens, Bacil-
lus indicus, Bacillus cecembensis, Enterobacter cloacae,
Geobacter spp., Arthrobacter gangotriensis, Corynebac-
terium sp. SH09, and Shewanella oneidensis. Likewise,
for the preparation of gold nanoparticles, several bacte-
rial species (such as Bacillus megaterium D01, Desulfo-
vibrio desulfuricans, E. coli DH5a, Bacillus subtilis 168,
Shewanella alga, Rhodopseudomonas capsulate, and
Plectonema boryanum UTEX 485) have been extensively
used. Information on the size, morphology, and applica-
tions of various nanoparticles is summarized in Table 1.
Singh et al. J Nanobiotechnol (2018) 16:84 Page 4 of 24

Table 1  Examples of metallic nanoparticles prepared in ILs by a chemical reduction method

S. no. Metal NPs Metal salt Reducing agent Ionic liquid Size (nm) References

1 Ag AgBF4 H2, 85 °C, 4 atm [BMIm][BF4] 0.8–2.8 [148]

BIm as scavenger [BMIm][PF6] 1.3–4.4
2 Ag AgBF4 H2 [BMIm][BF4] ~ 9 (DLS) [149]
[BMpy][TfO] ~ 11 (DLS)
3 Ag AgBF4 [BMIm][BH4] [BMIm][BF4] purified and ­H2O 0.8–4.4 [47]
4.0
0.9–4.5
4 Ag AgNO3 Tween 85 [BMIm][PF6] 3–10 [150]
5 Au HAuCl4 Ascorbic acid [BMIm] ­[C12H25OSO3] (lauryl sulfate) 20–50 [151]
6 Au HAuCl4 NaBH4 [ShexMIm][Cl] 5 [152]
7 Au HAuCl4 NaBH4 [BMIm][BF4] in a microfluidic reactor 0.5–4 [153]
8 Au HAuCl4-3H2O Glycerol [EMIm][TfO], ­[EMIm][MeSO3] 5–7 low temp. 5–7 [154]
aggregate at higher
temp.
9 HAuBr4 Me2NCHO (DMF) [Me2NH2][Me2NCO2] with small amounts of DMF 2–4 [155]
10 Cu Cu(OAc)2-H2O H2NNH2-H2O [BMIm][BF4] 80–130 [156]
(hydrazine
hydrate)

Fungi biosynthesis techniques employing plant extracts have

Fungi-mediated biosynthesis of metal/metal oxide nano-
particles is also a very efficient process for the genera-
tion of monodispersed nanoparticles with well-defined
morphologies. They act as better biological agents for the
preparation of metal and metal oxide nanoparticles, due
to the presence of a variety of intracellular enzyme [23].
Competent fungi can synthesize larger amounts of nano-
particles compared to bacteria [24]. Moreover, fungi have
many merits over other organisms due to the presence
of enzymes/proteins/reducing components on their cell
surfaces [25]. The probable mechanism for the forma-
tion of the metallic nanoparticles is enzymatic reduction
(reductase) in the cell wall or inside the fungal cell. Many
fungal species are used to synthesize metal/metal oxide
nanoparticles like silver, gold, titanium dioxide and zinc
oxide, as discussed in Table 1.
Yeast
Yeasts are single-celled microorganisms present in
eukaryotic cells. A total of 1500 yeast species have been
identified [26]. Successful synthesis of nanoparticles/
nanomaterials via yeast has been reported by numerous
research groups. The biosynthesis of silver and gold nan-
oparticles by a silver-tolerant yeast strain and Saccharo-
myces cerevisiae broth has been reported. Many diverse
species are employed for the preparation of innumerable
metallic nanoparticles, as discussed in Table 1.
Plants
Plants have the potential to accumulate certain amounts
of heavy metals in their diverse parts. Consequently,
gained increased consideration as a simple, efficient,
cost effective and feasible methods as well as an excellent
alternative means to conventional preparation methods
for nanoparticle production. There are various plants
that can be utilized to reduce and stabilize the metal-
lic nanoparticles in “one-pot” synthesis process. Many
researchers have employed green synthesis process for
preparation of metal/metal oxide nanoparticles via plant
leaf extracts to further explore their various applications.
Plants have biomolecules (like carbohydrates, pro-
teins, and coenzyme) with exemplary potential to reduce
metal salt into nanoparticles. Like other biosynthesis
processes, gold and silver metal nanoparticles were first
investigated in plant extract-assisted synthesis. Various
plants [including aloe vera (Aloe barbadensis Miller), Oat
(Avena sativa), alfalfa (Medicago sativa), Tulsi (Osimum
sanctum), Lemon (Citrus limon), Neem (Azadirachta
indica), Coriander (Coriandrum sativum), Mustard
(Brassica juncea) and lemon grass (Cymbopogon flexuo-
sus)] have been utilized to synthesize silver nanoparticles
and gold nanoparticles, as listed in Table  2. The major
part of this type of research has explored the ex vivo syn-
thesis of nanoparticles, while metallic nanoparticles can
be formed in living plants (in vivo) by reducing metal
salt ions absorbed as soluble salts. The in  vivo synthesis
of nanoparticles like zinc, nickel, cobalt, and copper was
also observed in mustard (Brassica juncea), alfalfa (Med-
icago sativa), and sunflower (Helianthus annuus) [27].
Also, ZnO nanoparticles have been prepared with a great
variety of plant leaf extracts such as coriander (Corian-
drum sativum) [28], crown flower (Calotropis gigantean)
Singh et al. J Nanobiotechnol (2018) 16:84 Page 5 of 24

Table 2  Synthesis of metallic NPs from various biological species

Sr. no. Species Nanoparticles Size (nm) Morphology Application References

Bacteria
1 Bacillus cereus Silver 20–40 Spherical Antibacterial activity [157]
against Escherichia coli,
Pseudomonas aeruginosa,
Staphylococcus aureus, Sal-
monella typhi, and Klebsiella
pneumonia bacteria
2 Pseudomonas proteolytica, Silver 6–13 Spherical Antibacterial activity [158]
Bacillus cecembensis against A. kerguelensis, A.
gangotriensis, B. indicus, P.
antarctica, P. proteolytica,
and E. coli
3 Lactobacillus casei Silver 20–50 Spherical Drug delivery, cancer treat‑ [159]
ments, bio-labeling
4 Klebsiella pneumonia, Silver 28–122 Spherical Optical receptors, electrical [79]
Escherichia coli, Enterobacter batteries, antimicrobial
cloacae
5 Bacillus indicus Silver – – Antimicrobial, catalysis [160]
6 Plectonema boryanum UTEX Gold < 10–25 Cubic, octahedral – [161]
485
7 Bacillus subtilis 168 Gold 5–50 Hexagonal-octahedral – [162]
8 Bacillus megaterium D01 Gold < 2.5 Spherical Catalysis, biosensing [163]
9 Shewanella alga Gold pH 7: 10–20 Triangular – [164]
pH 2.5: 15–200
pH 2: 20
10 E. coli DH 5α Gold 8–25 Spherical Direct electrochemistry of [165]
hemoglobin
11 Desulfovvibrio desulfuricans Gold 20–50 Spherical Catalysis [166]
12 Rhodopseudomonas capsulate Gold 10–20 Cancer hyperthermia Triangular [167]
13 Magnetospirillum magneto- Iron Oxide 47 – Handle shaped cluster [168]
tacticum
14 Aquaspirillum magnetotacti- Iron Oxide 40–50 Octahedral prism – [169]
cum
15 Shewanella oneidensis Uranium oxide 1–5 – – [170]
16 Klebsiella aerogenes Cadmium sulfide 20–200 – – [171]
17 E. coli Cadmium sulfide 2–5 Fluorescent labels Wurtzite structures [23]
Fungus
1 Rhizopus nigricans Silver 35–40 Round Bactericidal, catalytic [172]
2 Verticillium Silver 21–25 Spherical Catalysis [173]
3 Aspergillus fumigates Silver 5–25 Spherical Coating for solar energy [174]
absorption and intercala‑
tion material for electrical
batteries
4 Phanerochaete chrysosporium Silver 50–200 Pyramidal Medical textiles for antimi‑ [175]
crobial activity
5 Aspergillus flavus Silver 1–8 – Isotropic [176]
6 Aspergillus niger Silver 20 Spherical Antibacterial agent [177]
7 Fusarium semitectum Silver 10–60 Crystalline spherical Biolabelling [178]
8 Cladosporium cladosporioides Silver 10–100 Spherical – [179]
9 Cariolus versicolor Silver 25–75 Spherical Water-soluble metallic cata‑ [180]
lysts, labels for living cells
and tissues
10 Fusarium solani Silver 5–35 Spherical Biolabeling, sensors, drug [181]
delivery
11 Penicillium brecompactum Silver 23–105 Crystalline spherical Antimicrobial agent [182]
12 Penicillium fellutanum Silver 5–25 Spherical Thin film and surface coating [183]
Singh et al. J Nanobiotechnol (2018) 16:84 Page 6 of 24

Table 2  (continued)
Sr. no. Species Nanoparticles Size (nm) Morphology Application References

13 Phoma glomerata Silver 60–80 Spherical Antimicrobial agent [184]

14 Alternata alternate Silver 20–60 spherical Antifungal agent [185]
15 Trichoderma viride Silver 5–40 Spherical Antimicrobial agent [186]
16 Verticillium luteoalbum Gold < 10 Triangular, hexagonal Optics, sensor, coatings [20]
17 Rhizopus stolonifer Silver, Gold 25–30, 1–5 Spherical – [187]
18 Trichothecium sp. Gold 10–25 Spherical, rod-like and – [188]
triangular 
19 Fusarium oxysporum Gold-silver alloy 8–14 Spherical Biomedical field [189]
20 Aspergillus terreus Zinc oxide 8 Spherical Catalysis, biosensing, drug [190]
delivery, molecular diag‑
nostics, solar cell, optoelec‑
tronics, cell labeling, and
imaging
21 Aspergillus flavus TFR7 Titanium dioxide 12–15 Spherical Plant nutrient fertilizer [191]
Yeast
1 MKY3 Silver 2–5 Hexagonal Coatings for solar energy [192]
absorption and intercala‑
tion material for electrical
batteries
2 Saccharimyces cerevisae broth Gold, silver 4–15 Spherical Catalysis [193]

[29], copper leaf (Acalypha indica) [30], China rose
(Hibiscus rosa-sinensis) [31], Green Tea (Camellia sin-
ensis) [32], and aloe leaf broth extract (Aloe barbadensis
Miller) [33]. Readers can refer to the work of Iravani [34]
for a comprehensive overview of plant materials utilized
for the biosynthesis of nanoparticles.
Solvent system‑based “green” synthesis
Solvent systems are a fundamental component in the
synthesis process, whether it is “green” synthesis or not.
Water is always considered an ideal and suitable solvent
system for synthesis processes. According to Sheldon,
“the best solvent is no solvent, and if a solvent is desirable
then water is ideal” [35]. Water is the cheapest and most
commonly accessible solvent on earth. Since the advent
of nanoscience and nanotechnology, the use of water as
a solvent for the synthesis of various nanoparticles has
been carried out. For instance, synthesized Au and Ag
nanoparticles at room temperature using gallic acid, a
bifunctional molecule, in an aqueous medium [36]. Gold
nanoparticles were produced via a laser ablation tech-
nique in an aqueous solution. The oxygen present in the
water leads to partial oxidation of the synthesized gold
nanoparticles, which finally enhanced its chemical reac-
tivity and had a great impact on its growth [37].
In the literature, “green” synthesis consists of two major
routes:
• Wherein water is used as a solvent system.
• Wherein a natural source/extract is utilized as the
main component.
Both of these routes have been covered in the coming
section according to the present literature. Hopefully, our
efforts will help researchers gain a better knowledge of
‘green’ synthesis methods, the role of toxic/non-toxic sol-
vents (or components), and renewable resources derived
from natural sources. Ionic and supercritical liquids are
one of the best examples in this emerging area. Ionic liq-
uids (ILs) are composed of ions that have melting points
below 100  °C. Ionic liquids are also acknowledged as
“room temperature ionic liquids.” Several metal nano-
particles (e.g., Au, Ag, Al, Te, Ru, Ir, and Pt) have been
synthesized in ionic liquids [38–41]. The process of nano-
particle synthesis is simplified since the ionic liquid can
serve as both a reductant and a protective agent.
ILs can be hydrophilic or hydrophobic depending
on the nature of the cations and anions. For example,
1-butyl-3-methyl imidazolium (Bmim) hexafluorophos-
phate (PF6) is hydrophobic, whereas its tetrafluoroborate
(BF4) analogue is hydrophilic. Since both species are ionic
in nature, they can act as catalysts [40, 42–45]. Bussamara
et al. have performed a comparative study by controlling
the synthesis of manganese oxide ­(Mn3O4) nanoparti-
cles using imidazolium ionic liquids and oleylamine (a
conventional solvent). They found that smaller sized
nanoparticles (9.9 ± 1.8  nm) were formed with better
dispersity in ionic liquids than in the oleylamine solvent
(12.1 ± 3.0  nm) [46]. Lazarus et  al. synthesized silver
Singh et al. J Nanobiotechnol (2018) 16:84
nanoparticles in an ionic liquid (BmimBF4). The synthe-
sized nanoparticles were in both smaller isotropic spheri-
cal and large-sized anisotropic hexagonal shaped forms
[47]. An electrochemical method was employed for this
purpose [48]. Ionic liquid was used in the electrolytic
reaction as a substitute for water without mechanical
stirring. For the first time, Kim et  al. developed a one-
phase preparation technique for gold (Au) and platinum
(Pt) nanoparticles by means of thiol-functionalized ionic
liquids (TFILs). TFILs acted as a stabilizing agent to pro-
duce crystalline structures with small sizes [49]. Dupont
et  al. used 1-n-butyl-3-methylimidazolium hexafluoro-
phosphate (which is room temperature ionic liquid) for
synthesizing Ir(0) nanoparticles by Ir(I) reduction. The
average size of synthesized nanoparticles was ~ 2  nm.
Interestingly, the ionic liquid medium is impeccable for
the production of recyclable biphasic catalytic systems
for hydrogenation reactions [50].
The benefits of using ionic liquids instead of other sol-
vents include the following. (a) Many metal catalysts,
polar organic compounds, and gases are easily dissolved
in ILs to support biocatalysts. (b) ILs have constructive
thermal stabilities to operate in a broad temperature
range. Most of these melt below room temperature and
begin to decompose above 300 or 400 °C. As such, they
allow a broader synthesis temperature range (e.g., three
to four times) than that of water. (c) The solubility prop-
erties of IL can be modulated by modifying the cations
and anions associated with them. (d) Unlike other polar
solvents or alcohols, ILs are non-coordinating. However,
they have polarities comparable to alcohol. (e) ILs do
not evaporate into the environment like volatile solvents
because they have no vapor pressure. (f ) ILs have dual
functionality because they have both cations and anions.
The problems associated with the biodegradability of
ionic liquids make them not acceptable for synthesis of
metallic nanoparticles. To diminish these non-biodegra-
dability issues, many new potentially benign ionic liquids
are being developed with maximum biodegradation effi-
ciency [51–54]. The innumerable ILs are used to synthe-
size various metallic nanoparticles as listed in Table 3.
Likewise, ordinary solvents can be converted into super
critical fluids at temperatures and pressures above critical
point. In the supercritical state, solvent properties such as
density, thermal conductivity, and viscosity are significantly
altered. Carbon dioxide is the most feasible super critical,
non-hazardous, and inert fluid [55, 56]. Also, supercriti-
cal water can serve as a good solvent system for several
reactions. As, water has critical temperature of 646 K and
pressure of 22.1  MPa [57]. Silver and copper NPs can be
synthesized in supercritical carbon dioxide [58]. Sue et al.
suggested that decreasing the solubility of metal oxides
around the critical point can lead to super saturation and
Page 7 of 24
the ultimate formation of nanoparticles [59]. Kim et al. syn-
thesized tungsten oxide (­WO3) and tungsten blue oxide
nanoparticles by using sub- and supercritical water and
methanol [60].
Stability and toxicity of the nanoparticles
The environmental distribution and transport of released
nanoparticles depend on their ability to make metastable
aqueous suspensions or aerosols in environmental fluids.
The stability of the nanoparticles in the environment can
therefore be evaluated by estimating their propensity to
aggregate or interact with the surrounding media. Aggre-
gation is a time-dependent phenomena associated with
the rate of particle collision while the stability of the sus-
pension is largely determined by the size of the particles
and affinity toward other environmental constituents. The
“green” synthesis of AgNPs from tea leaf extraction was
found to be stable after entering the aquatic environment
[61]. Likewise, the stability of AgNPs (in aqueous medium)
manufactured using plant extracts and plant metabolites
was confirmed from the resulting material [62]. Surface
complexation is also reported to affect the intrinsic stabil-
ity of nanoparticles by regulating its colloidal stability. The
nature and stability of nanoparticles were theoretically pre-
dicted through a mechanistic understanding of the surface
complexation processes [63]. The colloidal stability (or rate
of dissolution) of nanoparticles can be regulated by con-
trolling the particle size and surface capping or through
functionalization techniques [64, 65]).
Transformation of nanoparticles is an essential property
to consider when assessing their environmental impact
or toxicity. For instance, sulfurization of AgNPs greatly
reduced their toxicity due to the lower solubility of silver
sulfide [66]. For similar reasons, the use of biocompatible
stabilizing agents (e.g., biodegradable polymers and copol-
ymers) have opened up a “greener” avenue of nanomaterial
surface engineering. Such techniques can impart remark-
able stability, e.g., in situ synthesis of AuNPs capped with
Korean red ginseng root [67]. Apart from surface chemis-
try, other key structural features determining the nanoma-
terial toxicity are the size, shape, and composition of the
nanomaterials [68]. Toxicity analysis of AgNP synthesized
using plant leaf extracts showed enhanced seed germina-
tion rates in the AgNP chemical treatment for activation
than the corresponding control treatments [69]. However,
the mechanism of such rate enhancement effects was not
reported.
Mechanism of “green” synthesis for metals
and their oxide nanoparticles
Microorganism‑based mechanism
There are different mechanisms for the formation of nan-
oparticles using different microorganisms. First, metallic
Singh et al. J Nanobiotechnol (2018) 16:84 Page 8 of 24

Table 3  Green synthesis of metallic NPs from various plant extracts

Order Plant origin Nanoparticle Size (nm) Morphology Applications References

1 Aloe barbadensis Miller Gold and silver 10–30 Spherical, triangular Cancer hyperthermia, [194]
(Aloe vera) optical coatings
2 Aloe barbadensis Miller Indium oxide 5–50 Spherical Solar cells, gas sensors [32]
(Aloe vera)
3 Acalypha indica Silver 20–30 Spherical Antibacterial activity [195]
against water borne
pathogens
4 Apiin extracted from Silver and gold 39 Spherical, triangular, and Hyperthermia of cancer [196]
henna leaves quasi-spherical cells and IR-absorbing
optical coatings
5 Avena sativa (oat) Gold 5–20 (pH 3 and 4), Rod-shaped – [197]
6 Azadirachta indica Gold, silver and silver- 5–35 and 50–100 Spherical, triangular, Remediation of toxic [198]
(neem) gold alloys hexagonal metals
7 Camellia sinensis (black Gold and silver 20 Spherical, prism Catalysts, sensors [199]
tea leaf extracts)
8 Brassica juncea (mustard) Silver 2–35 Spherical – [200]
9 Cinnamomum camphora Gold and silver 55–80 Triangular, spherical (Au), – [85]
(camphor tree) and quasi-spherical
(Ag)
10 Carica papaya (papaya) Silver 60–80 Spherical – [86]
11 Citrus limon (lemon) Silver < 50 Spherical, spheroidal – [201]
12 Coriandrum sativum Gold 6.75–57.91 Spherical, triangular, Drug delivery, tissue/ [202]
(coriander) truncated triangular, tumor imaging, photo‑
decahedral thermal therapy
13 Cymbopogon flexuosus Gold 200–500 Spherical, triangular Infrared-absorbing opti‑ [203]
(lemongrass) cal coatings
14 Cycas sp. (cycas) Silver 2–6 Spherical – [204]
15 Diospyros kaki (persim‑ bimetallic gold/silver 50–500 Cubic – [205]
mon)
16 Emblica officinalis (indian Gold and silver (10–20) and (15–25) – – [206]
gooseberry)
17 Eucalyptus citriodora Silver 20 Spherical Antibacterial [207]
(neelagiri)
18 Eucalyptus hybrida Silver 50–150 Crystalline, spherical – [208]
(safeda)
19 Garcinia mangostana Silver 35 Spherical Antimicrobial activity [209]
(mangosteen) against E. coli and S.
aureus
20 Gardenia jasminoides Ellis Palladium 3–5 – Nanocatalysts for [210]
(gardenia) p-nitrotoluene hydro‑
genation
21 Syzygium aromaticum Gold 5-100 Irregular Detection and destruc‑ [211]
(clove buds) tion of cancer cells
22 Jatropha curcas (seed Silver 15–50 Spherical – [212]
extract)
23 Ludwigia adscendens Silver 100–400 Spherical – [213]
(ludwigia)
24 Medicago sativa (alfalfa) Gold 2–40 Irregular, tetrahedral, Labeling in structural [214–216]
hexagonal platelet, biology, paints
decahedral, icosa‑
hedral
25 Mentha piperita (pep‑ Silver 5–30 Spherical To kill microbes [217]
permint)
26 Medicago sativa (alfalfa) Iron oxide 2–10 Crystalline Cancer hyperthermia, [218]
drug delivery
27 Morus (mulberry) Silver 15–20 Spherical Antimicrobial activity [219]
against E. coli, B. subtilis
Singh et al. J Nanobiotechnol (2018) 16:84 Page 9 of 24

Table 3  (continued)
Order Plant origin Nanoparticle Size (nm) Morphology Applications References

27 Nelumbo nucifera (lotus) Silver 25–80 Spherical, triangular, Larvicidal activity against [220]
truncated triangular, malaria and filariasis
decahedral vectors
28 Ocimum sanctum (tulsi; Silver 10 ± 2 and 5 ± 1.5 nm Spherical Catalytic reduction [221]
root extract)
28 Ocimum sanctum (tulsi; Gold and silver 30 and 10–20 Crystalline, hexagonal, Biolabeling, biosensor [222]
leaf extract) triangular and spheri‑
cal
29 Pear fruit extract Gold 200–500 Triangular, hexagonal Catalysis, biosensing [223]
30 Pelargonium roseum Gold 2.5–27.5 Crystalline – [88]
(rose geranium)
31 Psidium guajava (guava) Gold 25–30 Mostly spherical – [224]
32 Sedum alfredii Hance Zinc oxide 53.7 Hexagonal wurtzite and Nanoelectronics [225]
pseudo-spherical
33 Tanacetum vulgare (tansy Gold and silver 11, 16 Triangular, spherical Antibacterial, sensors [226]
fruit)
34 Terminalia catappa Gold 10–35 Spherical Biomedical field [227]
(almond)

ions are captured on the surface or inside the microbial
cells, and then these arrested metal ions are reduced into
metal nanoparticles by the action of enzymes. Sneha et al.
[70] described the mechanism of microorganism-assisted
silver and gold nanoparticles formed via Verticillium sp.
or algal biomass based on the following hypothesis. (a)
First, the silver or gold ions were captured on the surface
of fungal cells via electrostatic interactions between ions
and negatively charged cell wall enzymes. (b) Then, silver
or gold ions were bioreduced into silver or gold nuclei,
which subsequently grew. The two key aspects in the
biosynthesis of nanoparticles are NADH (nicotinamide
adenine dinucleotide) and NADH-dependent nitrate
reductase. Kalishwaralal et  al. [71] demonstrated that
the nitrate reductase was responsible for the production
of bioreduced silver nanoparticles by B. licheniformis.
Nonetheless, the bioreduction mechanisms associated
with the production of metal salt ions and the resulting
metallic nanoparticles formed by microorganisms remain
unexplored.
Plant leaf extract‑based mechanism
For nanoparticle synthesis mediated by plant leaf extract,
the extract is mixed with metal precursor solutions at
different reaction conditions [72]. The parameters deter-
mining the conditions of the plant leaf extract (such
as types of phytochemicals, phytochemical concentra-
tion, metal salt concentration, pH, and temperature) are
admitted to control the rate of nanoparticle formation as
well as their yield and stability [73]. The phytochemicals
present in plant leaf extracts have uncanny potential to
reduce metal ions in a much shorter time as compared to
fungi and bacteria, which demands the longer incubation
time [74]. Therefore, plant leaf extracts are considered
to be an excellent and benign source for metal as well as
metal oxide nanoparticle synthesis. Additionally, plant
leaf extract play a dual role by acting as both reducing
and stabilizing agents in nanoparticles synthesis process
to facilitate nanoparticles synthesis [75]. The composi-
tion of the plant leaf extract is also an important factor in
nanoparticle synthesis, for example different plants com-
prise varying concentration levels of phytochemicals [76,
77]. The main phytochemicals present in plants are fla-
vones, terpenoids, sugars, ketones, aldehydes, carboxylic
acids, and amides, which are responsible for bioreduction
of nanoparticles [78].
Flavonoids contain various functional groups, which
have an enhanced ability to reduce metal ions. The reac-
tive hydrogen atom is released due to tautomeric trans-
formations in flavonoids by which enol-form is converted
into the keto-form. This process is realized by the reduc-
tion of metal ions into metal nanoparticles. In sweet basil
(Ocimum basilicum) extracts, enol- to keto-transforma-
tion is the key factor in the synthesis of biogenic silver
nanoparticles [79]. Sugars such as glucose and fructose
exist in plant extracts can also be responsible for the
formation of metallic nanoparticles. Note that glucose
was capable of participating in the formation of metal-
lic nanoparticles with different size and shapes, whereas
fructose-mediated gold and silver nanoparticles are
monodisperse in nature [80].
An FTIR analysis of green synthesized nanoparticles
via plant extracts confirmed that nascent nanoparticles
were repeatedly found to be associated with proteins
Singh et al. J Nanobiotechnol (2018) 16:84
Fig. 3  Schematic for the reduction of Au and Ag ions [89]
[81]. Also, amino acids have different ways of reducing
the metal ions. Gruen et  al. [82] observed that amino
acids (viz cysteine, arginine, lysine, and methionine are
proficient in binding with silver ions. Tan et al. [83] tested
all of the 20 natural α-amino acids to establish their effi-
cient potential behavior towards the reduction of ­Au0
metal ions.
Plant extracts are made up of carbohydrates and pro-
teins biomolecules, which act as a reducing agent to pro-
mote the formation of metallic nanoparticles [34]. Also,
the proteins with functionalized amino groups (–NH2)
available in plant extracts can actively participate in the
reduction of metal ions [84]. The functional groups (such
as –C–O–C–, –C–O–, –C=C–, and –C=O–) present in
phytochemicals such as flavones, alkaloids, phenols, and
anthracenes can help to generate metallic nanoparticles.
According to Huang et  al. [85], the absorption peaks of
FTIR spectra at (1) 1042 and 1077, (2) 1606 and 1622, and
Page 10 of 24
(3) 1700–1800  cm−1 imply the stretching of (1) –C–O–
C– or –C–O–, (2) –C=C– and (3) –C=O, respectively.
Based on FTIR analysis, they confirmed that functional
groups like –C–O–C–, –C–O–, –C=C–, and –C=O,
are the capping ligands of the nanoparticles [86]. The
main role of the capping ligands is to stabilize the nano-
particles to prevent further growth and agglomeration.
Kesharwani et  al. [87] covered photographic films using
an emulsion of silver bromide. When light hit the film,
the silver bromide was sensitized; this exposed film was
placed into a solution of hydroquinone, which was fur-
ther oxidized to quinone by the action of sensitized sil-
ver ion. The silver ion was reduced to silver metal, which
remained in the emulsion.
Based on the chemistry of photography, we assumed
that hydroquinone or plastohydroquinone or quinol
(alcoholic compound) serve as a main reducing agent
Singh et al. J Nanobiotechnol (2018) 16:84
Fig. 4  Mechanism of nanoparticle formation by plant leaf extract [228]
for the reduction of silver ions to silver nanoparticles
through non-cyclic photophosphorylation [87]. Thus,
this experiment proves that the biomolecules and hetero-
cyclic compounds exist in plant extract were accountable
for the extracellular synthesis of metallic nanoparticles by
plants. It has already been well established that numer-
ous plant phytochemicals including alkaloids, terpe-
noids, phenolic acids, sugars, polyphenols, and proteins
play a significant role in the bioreduction of metal salt
into metallic nanoparticles. For instance, Shanakr et  al.
[88] confirmed that the terpenoids present in geranium
leaf extract actively take part in the conversion of sil-
ver ions into nanoparticles. Eugenol is a main terpenoid
component of Cinnamomum zeylanisum (cinnamon)
extracts, and it plays a crucial role for the bioreduction
of ­HAuCl4 and A ­ gNO3 metal salts into their respective
metal nanoparticles. FTIR data showed that –OH groups
originating from eugenol disappear during the formation
of Au and Ag nanoparticles. After the formation of Au
nanoparticles, carbonyl, alkenes, and chloride functional
groups appeared. Several other groups [e.g., R–CH and
–OH (aqueous)] were also found both before and after
the production of Au nanoparticles [89]. Thus, they pro-
posed the possible chemical mechanism shown in Fig. 3.
Nonetheless, the exact fundamental mechanism for
metal oxide nanoparticle preparation via plant extracts
Page 11 of 24
is still not fully tacit. In general, there are three phases
of metallic nanoparticle synthesis from plant extracts:
(1) the activation phase (bioreduction of metal ions/salts
and nucleation process of the reduced metal ions), (2) the
growth phase (spontaneous combination of tiny particles
with greater ones) via a process acknowledged as Ost-
wald ripening, and (3) the last one is termination phase
(defining the final shape of the nanoparticles) [90, 91].
The process of nanoparticle formation by plant extract is
depicted in Fig. 4 [92].
Environmental remediation applications
Antimicrobial activity
Various studies have been carried out to ameliorate
antimicrobial functions because of the growing micro-
bial resistance towards common antiseptic and antibi-
otics. According to in  vitro antimicrobial studies, the
metallic nanoparticles effectively obstruct the several
microbial species [93]. The antimicrobial effectiveness
of the metallic nanoparticles depends upon two impor-
tant parameters: (a) material employed for the synthe-
sis of the nanoparticles and (b) their particle size. Over
the time, microbial resistance to antimicrobial drugs
has become gradually raised and is therefore a consid-
erable threat to public health. For instance, antimicro-
bial drug resistant bacteria contain methicillin-resistant,
Singh et al. J Nanobiotechnol (2018) 16:84 Page 12 of 24

Fig. 5  Schematic for the multiple antimicrobial mechanisms in different metal nanoparticles against microbial cells [96]

Fig. 6  Various mechanisms of antimicrobial activity of metal nanoparticles [93]

Singh et al. J Nanobiotechnol (2018) 16:84
Table 4  Multiple mechanisms of antimicrobial action for various metallic nanoparticles [96]
S. no. Nanoparticles
1 Nitric oxide-releasing nanoparticles (NO NPs)
2 Chitosan-containing nanoparticles
3 Silver-containing nanoparticles (Ag NPs)
4 Zinc oxide-containing nanoparticles (ZnO NPs)
5 Copper-containing nanoparticles
6 Titanium dioxide-containing nanoparticles ­( TiO2 NPs) (a) In the photocatalysis process, ­TiO2 NPs generate ROS, including hydrogen peroxide
7 Magnesium-containing nanoparticles
sulfonamide-resistant, penicillin-resistant, and vancomy-
cin-resistant properties [94]. Antibiotics face many cur-
rent challenges such as combatting multidrug-resistant
mutants and biofilms. The effectiveness of antibiotic is
likely to decrease rapidly because of the drug resistance
capabilities of microbes. Hence, even when bacteria are
treated with large doses of antibiotics, diseases will per-
sist in living beings. Biofilms are also an important way
of providing multidrug resistance against heavy doses of
antibiotics. Drug resistance occurs mainly in infectious
diseases such as lung infection and gingivitis [95]. The
most promising approach for abating or avoiding micro-
bial drug resistance is the utilization of nanoparticles.
Due to various mechanisms, metallic nanoparticles can
preclude or overwhelm the multidrug-resistance and bio-
film formation, as described in Figs. 5 and 6.
Various nanoparticles employ multiple mechanisms
concurrently to fight microbes [e.g., metal-containing
nanoparticles, NO-releasing nanoparticles (NO NPs),
and chitosan-containing nanoparticles (chitosan NPs)].
Nanoparticles can fight drug resistance because they
operate using multiple mechanisms. Therefore, microbes
must simultaneously have multiple gene mutations in
their cell to overcome the nanoparticle mechanisms.
Page 13 of 24
Multiple mechanisms
NO forms reactive nitrogen oxide intermediates (RNOS) by reacting with superoxide
­(O2−)
(a) RNOS cause direct nitrosative damage to DNA, including causing strand breaks,
formation of abasic sites and depleting the Fe in a bacterial cell
(b) RNOS inactivate zinc metalloproteins, which results in inhibition of microbial cellular
respiration
(c) RNOS also cause lipid peroxidation
(a) Due to its positive charge, chitosan binds with DNA in bacterial and fungal cells,
thereby inhibiting transcription of mRNA resulting in protein translation
(c) Chitosan also decreases the activities of metalloproteins
The antimicrobial activity of silver (Ag) is due to its ­Ag+ ions
(a) ­Ag+ inhibits the electron transport chain of microbes
(b) ­Ag+ damages DNA and RNA by binding with them
(c) ­Ag+ also inhibits cell division by inhibiting DNA replication
(d) ­Ag+ ions form ROS, which are toxic to both bacterial cells and eukaryotic host cells
(a) ZnO NPs destroy both lipids and the proteins of the membrane, which can cause cell
death
(b) ZnO NPs also form ­Zn2+ ions and ROS, including hydrogen peroxide ­(H2O2),which
damage the bacterial cell
(a) Copper interacts with amine and carboxyl groups, which are present on microbes
such as B. subtilis
­ u2+ ions can produce ROS
(b) Higher concentrations of C
­(H2O2) and hydroxyl radicals (·OH), upon exposure to near-UV and UVA radiation
(a) ­MgX2 NPs also cause lipid peroxidation of the microbial cell envelope by generating
ROS
(b) ­MgF2 NPs can cause lipid peroxidation and a drop in cytoplasmic pH, which raises
membrane potential
However, simultaneous multiple biological gene muta-
tions in the same cell are unlikely [96].
Multiple mechanisms observed in nanoparticles are
discussed in Table  4. Silver nanoparticles are the most
admired inorganic nanoparticles, and they are utilized
as efficient antimicrobial, antifungal, antiviral, and anti-
inflammatory agents [97]. According to a literature sur-
vey, the antimicrobial potential of silver nanoparticles
can be described in the following ways: (1) denatura-
tion of the bacterial outer membrane [98], (2) genera-
tion of pits/gaps in the bacterial cell membrane leading
to fragmentation of the cell membrane [99, 100], and (3)
interactions between Ag NPs and disulfide or sulfhydryl
groups of enzymes disrupt metabolic processes; this step
leads to cell death [101]. The shape-dependent antimi-
crobial activity was also examined. According to Pal et al.
[102], truncated triangular nanoparticles are highly reac-
tive in nature because their high-atom-density surfaces
have enhanced antimicrobial activity.
The synthesis of Au nanoparticles is highly useful in the
advancement of effective antibacterial agents because of
their non-toxic nature, queer ability to be functionalized,
polyvalent effects, and photo-thermal activity [103–105].
However, the antimicrobial action of gold nanoparticles
is not associated with the production of any reactive
Singh et al. J Nanobiotechnol (2018) 16:84 Page 14 of 24

Fig. 7  Schematic for the antimicrobial activity for the five bacterial strains: a Staphylococcus aureus, b Klebsiella pneumonia, c Pseudomonas
aeruginosa, d Vibrio cholera, and e Proteus vulgaris. Numbers of 1 through 6 inside each strain denote: (1) nickel chloride, (2) control ciprofloxacin,
(3) Desmodium gangeticum root extract, (4) negative control, (5) nickel NPs prepared by a green method, and (6) nickel NPs prepared by a chemical
method [229]

oxygen species-related process [106]. To investigate the
antibacterial potential of the Au nanoparticles, research-
ers attempted to attach nanoparticles to the bacterial
membrane followed by modifying the membrane poten-
tial, which lowered the ATP level. This attachment also
inhibited tRNA binding with the ribosome [106]. Azam
et  al. [107] examined the antimicrobial potential of zinc
oxide (ZnO), copper oxide (CuO), and iron oxide ­(Fe2O3)
nanoparticles toward gram-negative bacteria (Escherichia
coli, Pseudomonas aeruginosa) and gram-positive bacte-
ria (Staphylococcus Aureus and Bacillus subtilis). Accord-
ingly, the most intense antibacterial activity was reported
for the ZnO nanoparticles. In contrast, F ­ e2O3 nanoparti-
cles exhibited the weakest antibacterial effects. The order
of antibacterial activities of nanoparticles was found to
be as ZnO (19.89 ± 1.43 nm), CuO (29.11 ± 1.61 nm), and
­Fe2O3 (35.16 ± 1.47 nm). These results clearly depicts that
the size of the nanoparticles also play a momentous role
in the antibacterial potential of each sample [107]. The
anticipated mechanism of antimicrobial action of ZnO
nanoparticles is: (1) ROS generation, (2) zinc ion release
on the surface, (3) membrane dysfunction, and (4) entry
into the cell. Also, the antimicrobial potential of ZnO
nanoparticles is concentration and surface area depend-
ent [108]. Mahapatra et  al. [109] determined the anti-
microbial action of copper oxide nanoparticles towards
several bacterial species such as Klebsiella pneumoniae,
P. aeruginosa, Shigella Salmonella paratyphi s. They
found that CuO nanoparticles exhibited suitable antibac-
terial activity against those bacteria. It was assumed that
nanoparticles should cross the bacterial cell membrane
to damage the crucial enzymes of bacteria, which further
induce cell death. For instance, green synthesized nano-
particles show enhanced antimicrobial activity compared
to chemically synthesized or commercial nanoparti-
cles. This is because the plants [such as Ocimum sanc-
tum (Tulsi) and Azadirachta indica (neem)] employed
for synthesis of nanoparticles have medicinal properties
[110, 111]. For example, green synthesized silver nano-
particles showed an efficient and large zone of clearance
against various bacterial strains compared to commercial
silver nanoparticles (Fig. 7) [112].
Singh et al. J Nanobiotechnol (2018) 16:84
Fig. 8  Schematic of the metallic NP-mediated catalytic reduction of 4-nitrophenol to 4-aminophenol [120]
Catalytic activity
4-Nitrophenol and its derivatives are used to manufac-
ture herbicides, insecticides, and synthetic dyestuffs,
and they can significantly damage the ecosystem as com-
mon organic pollutants of wastewater. Due to its toxic
and inhibitory nature, 4-nitrophenol is a great environ-
mental concern. Therefore, the reduction of these pol-
lutants is crucial. The 4-nitrophenol reduction product,
4-aminophenol, has been applied in diverse fields as an
intermediate for paracetamol, sulfur dyes, rubber anti-
oxidants, preparation of black/white film developers,
corrosion inhibitors, and precursors in antipyretic and
analgesic drugs [113, 114]. The simplest and most effec-
tive way to reduce 4-nitrophenol is to introduce ­NaBH4
as a reductant and a metal catalyst such as Au NPs [115],
Ag NPs [116], CuO NPs [117], and Pd NPs [118]. Metal
NPs exhibit admirable catalytic potential because of the
high rate of surface adsorption ability and high surface
area to volume ratio. Nevertheless, the viability of the
reaction declines as a consequence of the substantial
potential difference between donor ­(H3BO3/NaBH4) and
acceptor molecules (nitrophenolate ion), which accounts
for the higher activation energy barrier.
Metallic NPs can promote the rate of reaction by
increasing the adsorption of reactants on their surface,
thereby diminishing activation energy barriers [119,
120] (Fig. 8). The UV–visible spectrum of 4-nitrophenol
Page 15 of 24
was characterized by a sharp band at 400 nm as a nitro-
phenolate ion was produced in the presence of NaOH.
The addition of Ag NPs (synthesized by Chenopodium
aristatum L. stem extract) to the reaction medium led to
a fast decay in the absorption intensity at 400 nm, which
was concurrently accompanied by the appearance of a
comparatively wide band at 313  nm, demonstrating the
formation of 4-aminophenol [121] (Fig. 9).
Removal of pollutant dyes
Cationic and anionic dyes are a main class of organic pol-
lutants used in various applications [122]. Organic dyes
play a very imperative role due to their gigantic demand
in paper mills, textiles, plastic, leather, food, printing,
and pharmaceuticals industries. In textile industries,
about 60% of dyes are consumed in the manufacturing
process of pigmentation for many fabrics [123]. After
the fabric process, nearly 15% of dyes are wasted and are
discharged into the hydrosphere, and they represent a
significant source of pollution due to their recalcitrance
nature [124]. The pollutants from these manufacturing
units are the most important sources of ecological pol-
lution. They produce undesirable turbidity in the water,
which will reduce sunlight penetration, and this leads to
the resistance of photochemical synthesis and biological
attacks to aquatic and marine life [125–127]. Therefore,
the management of effluents containing dyes is one of the
Singh et al. J Nanobiotechnol (2018) 16:84 Page 16 of 24

Fig. 9  UV-visible spectra illustrating Chenopodium aristatum L. stem extract synthesized Ag NP-mediated catalytic reduction of 4-NP to 4-AP at
three different temperatures a 30 °C, b 50 °C, and c 70 °C. Reduction in the absorption intensity of the characteristic nitrophenolate band at 400 nm
accompanied by concomitant appearance of a wider absorption band at 313 nm indicates the formation of 4-AP [121]

daunting challenge in the field of environmental chemis-
try [128].
The need for hygienic and safe drinking water is
increasing day by day. Considering this fact, the use of
metal and metal oxide semiconductor nanomaterials
for oxidizing toxic pollutants has become of great inter-
est in recent material research fields [129–131]. In the
nano regime, semiconductor nanomaterials have supe-
rior photocatalytic activity relative to the bulk materi-
als. Metal oxide semiconductor nanoparticles (like ZnO,
­TiO2, ­SnO2, ­WO3, and CuO) have been applied preferen-
tially for the photocatalytic activity of synthetic dyes [31,
132–134]. The merits of these nanophotocatalysts (e.g.,
ZnO and T ­ iO2 nanoparticles) are ascribable to their high
surface area to mass ratio to enhance the adsorption of
organic pollutants. The surface energy of the nanoparti-
cles increases due to the large number of surface reactive
sites available on the nanoparticle surfaces. This leads to
an increase in rate of contaminant removal at low con-
centrations. Consequently, a lower quantity of nanocata-
lyst will be required to treat polluted water relative to the
bulk material [135–138]. Like metal oxide nanoparticles,
metal nanoparticles also show enhanced photocatalytic
degradation of various pollutant dyes; for example, silver
nanoparticles synthesized from Z. armatum leaf extract
were utilized for the degradation of various pollutant
dyes [127] (Fig. 10).
Heavy metal ion sensing
Heavy metals (like Ni, Cu, Fe, Cr, Zn, Co, Cd, Pb, Cr,
Hg, and Mn) are well-known for being pollutants in air,
soil, and water. There are innumerable sources of heavy
metal pollution such as mining waste, vehicle emissions,
natural gas, paper, plastic, coal, and dye industries [139].
Some metals (like lead, copper, cadmium, and mercury
ions) shows enhanced toxicity potential even at trace
Singh et al. J Nanobiotechnol (2018) 16:84 Page 17 of 24

Fig. 10  Schematic for the reduction of a safranine O, b methyl red, c methyl orange, and d methylene blue dyes using silver NPs synthesized from
Z. armatum leaf extract by metallic nanoparticles [136]

ppm levels [140, 141]. Therefore, the identification of lead ions ­(Hg2+ and ­Pb2+). Also, AgNPs prepared from
toxic metals in the biological and aquatic environment pepper seed extract and green tea extract (GT-AgNPs)
has become a vital need for proper remedial processes ­ g2+, ­Pb2+, and
showed selective sensing properties for H
[142–144]. Conventional techniques based on instru- 2+
­Zn ions [147] (Fig. 11).
mental systems generally offer excellent sensitivity in
multi-element analysis. However, experimental set ups
Conclusion and future prospects
to perform such analysis are highly expensive, time-con-
‘Green’ synthesis of metal and metal oxide nanoparti-
suming, skill-dependent, and non-portable.
cles has been a highly attractive research area over the
Due to the tunable size and distance-dependent opti-
last decade. Numerous kinds of natural extracts (i.e.,
cal properties of metallic nanoparticles, they have been
biocomponents like plant, bacteria, fungi, yeast, and
preferably employed for the detection of heavy metal ions
plant extract) have been employed as efficient resources
in polluted water systems [145, 146]. The advantages of
for the synthesis and/or fabrication of materials.
using metal NPs as colorimetric sensors for heavy metal
Among them, plant extract has been proven to pos-
ions in environmental systems/samples include simplic-
sess high efficiency as stabilizing and reducing agents
ity, cost effectiveness, and high sensitivity at sub ppm
for the synthesis of controlled materials (i.e., controlled
levels. Karthiga et  al. [147] synthesized AgNPs using
shapes, sizes, structures, and other specific features).
various plant extracts used as colorimetric sensors for
This review article was organized to encompass the
heavy metal ions like cadmium, chromium, mercury,
‘state of the art’ research on the ‘green’ synthesis of
calcium, and zinc ­(Cd2+, ­Cr3+, ­Hg2+, ­Ca2+, and ­Zn2+)
metal/metal oxide nanoparticles and their use in envi-
in water. Their as-synthesized Ag nanoparticles showed
ronmental remediation applications. Detailed synthesis
colorimetric sensing of zinc and mercury ions (­ Zn2+ and
mechanisms and an updated literature study on the role
­Hg2+). Likewise, AgNPs synthesized using mango fresh
of solvents in synthesis have been reviewed thoroughly
leaves and dried leaves (fresh, MF-AgNPs and sun-dried,
based on the literature available to help encounter the
MD-AgNPs) exhibited selective sensing for mercury and
Singh et al. J Nanobiotechnol (2018) 16:84 Page 18 of 24

Fig. 11  Schematic of metal removal using metal oxides prepared by green synthesis. Left—a digital images and b absorption spectra of
neem bark extract-mediated silver NPs (NB-AgNPs) with different metal ions and concentration-dependent studies of c ­Hg2+ and d ­Zn2+.
Right—a digital images and b absorption spectra of fresh mango leaf extract-mediated silver NPs (MF-AgNPs) with different metal ions and c
concentration-dependent studies of P­ b2+ removal [147]

existing problems in ‘green’ synthesis. In summary,
future research and development of prospective ‘green’
materials/nanoparticle synthesis should be directed
toward extending laboratory-based work to an indus-
trial scale by considering traditional/present issues,
especially health and environmental effects. Neverthe-
less, ‘green’ material/nanoparticle synthesis based on
biocomponent-derived materials/nanoparticles is likely
to be applied extensively both in the field of environ-
mental remediation and in other important areas like
pharmaceutical, food, and cosmetic industries. Bio-
synthesis of metals and their oxide materials/nanopar-
ticles using marine algae and marine plants is an area
that remains largely unexplored. Accordingly, ample
possibilities remain for the exploration of new green
preparatory strategies based on biogenic synthesis.
Authors’ contributions
JS, KHK and PK made substantial contributions to interpretation of literature;
drafted the article and revised it critically. All made substantial contributions to
draft the article and revised it critically for important intellectual content and
gave approval to the submitted manuscript. All authors read and approved
the final manuscript.
Author details
1
 Department of Nanotechnology, Sri Guru Granth Sahib World University,
Fatehgarh Sahib, Punjab 140406, India. 2 Department of Chemical, Biologi‑
cal & Macromolecular Sciences, S. N. Bose National Centre for Basic Sciences,
Block JD, Sector III, Salt Lake, Kolkata 700 098, India. 3 Department of Civil &
Environmental Engineering, Hanyang University, Seoul 04763, South Korea.
4
 Department of Nano Science and Materials, Central University of Jammu,
Jammu, J & K 180011, India.
Singh et al. J Nanobiotechnol (2018) 16:84
Acknowledgements
The corresponding author (KHK) acknowledges a supporting Grant from
the National Research Foundation of Korea (NRF) funded by the Ministry of
Science, ICT, & Future Planning (No. 2016R1E1A1A01940995). Dr. Pawan Kumar
would like to thank SERB and UGC, New Delhi, for the ‘Empowerment and
Equity Opportunities for Excellence in Science’ video file No. EEQ/2016/00484
and the UGC-BSR Start Up-Research Project.
Competing interests
The authors declare that they have no competing interests.
Availability of data and materials
Without restrictions.
Consent for publication
Not applicable.
Ethics approval and consent to participate
All authors read and approved the final manuscript.
Funding
The corresponding author (KHK and PK) acknowledges a supporting grant
from the National Research Foundation of Korea (NRF) funded by the Ministry
of Science, ICT, & Future Planning (No. 2016R1E1A1A01940995) and ‘Empow‑
erment and Equity Opportunities for Excellence in Science’ video file No.
EEQ/2016/00484 and the UGC-BSR Start Up-Research Project.
Publisher’s Note
Springer Nature remains neutral with regard to jurisdictional claims in pub‑
lished maps and institutional affiliations.
Received: 26 August 2018 Accepted: 8 October 2018
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